EP1162078B1 - Matériau pour l'enregistrement d'images et absorbeur d'infrarouge - Google Patents

Matériau pour l'enregistrement d'images et absorbeur d'infrarouge Download PDF

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Publication number
EP1162078B1
EP1162078B1 EP01112937A EP01112937A EP1162078B1 EP 1162078 B1 EP1162078 B1 EP 1162078B1 EP 01112937 A EP01112937 A EP 01112937A EP 01112937 A EP01112937 A EP 01112937A EP 1162078 B1 EP1162078 B1 EP 1162078B1
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EP
European Patent Office
Prior art keywords
image
groups
alkyl group
group
fluorine
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EP01112937A
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German (de)
English (en)
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EP1162078A2 (fr
EP1162078A3 (fr
Inventor
Ippei Nakamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >CH- groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the present invention relates to a positive or negative image-formation material which can be recorded image-wise by exposure to an infrared laser and in which solubility of a recording layer at exposed portions changes, and to an infrared absorber which can be suitably used in the image-formation material. More particularly, the present invention relates to an image-formation material with an infrared layer, which can be recorded by exposure to an infrared laser or the like in the near-infrared range, and particularly which is suitable for a planographic printing plate used for so-called direct plate formation which can provide plate formation directly from digital signals of computers and the like, and to an infrared absorber having a surface orientation group, which absorber is suitable for application in the image-formation material.
  • JP-A No. 7-285275 discloses a positive-type planographic printing material for infrared lasers used in direct plate formation.
  • This invention is an image-recording material obtained by adding to an alkaline aqueous solution-soluble resin a substance which absorbs light and generates heat, and a positive photosensitive compound such as a quinonediazide compound or the like.
  • the positive photosensitive compound acts in image portions as a solution inhibitor that substantially decreases solubility of the alkaline aqueous solution-soluble resin, and is decomposed in non-image portions by heat, leading to a loss of solution-inhibiting ability. Resultantly, the positive photosensitive compound can be removed by development, to form an image.
  • WO97/39894 describes that a composition using a cationic infrared absorber as an agent to suppress dissolution of an alkaline water-soluble polymer shows a positive action. This positive action is such that an infrared absorber absorbs laser light and an effect of suppressing dissolution of a polymer film at irradiated portions is reduced by generated heat, to form an image.
  • a method for forming negative images there is a recording method in which a polymerization reaction is allowed to occur using, as an initiator, radicals generated by light or heat. The reaction cures a recording layer at exposed portions, forming image portions.
  • a photosensitive layer there are known technologies using, as a photosensitive layer, photopolymerizable or heat-polymerizable compositions as described in JP-A Nos. 8-108621 and 9-34110.
  • EP 0 901 902 A discloses a positive photosensitive composition for use with an infrared laser, comprising an alkali aqueous solution soluble polymer compound (A), a compound (B) which is compatible with the alkali aqueous solution soluble polymer compound, thereby lowering the solubility of the alkali aqueous solution soluble polymer compound in an alkali aqueous solution, the effect of lowering the solubility being reduced by heating, and a compound (C) which generates heat upon absorption of light, wherein the thermal decomposition temperature of each of compound (A), compound (B), and compound (C) is higher than 150°C.
  • EP 1 093 934 A discloses a photosensitive composition
  • a photosensitive composition comprising an infrared absorbing agent and a polymer compound which is insoluble in water and soluble in aqueous alkali solution and becoming soluble in an aqueous alkali solution by radiation of an infrared laser.
  • EP 1 053 868 A discloses a photosensitive composition, comprising: a macromolecular compound having alkali-soluble groups; and a compound that is capable of absorbing infrared rays and that acts on the alkali-soluble groups of said macromolecular compound and substantially suppresses the solubility of said macromolecular compound in an alkali aqueous solution, wherein the infrared ray-absorbable compound absorbs infrared rays and generates heat when subjected to infrared irradiation, and the macromolecular compound becomes substantially soluble in an alkali aqueous solution as a result of the action of the heat.
  • an object of the present invention is to provide an image formation material having high sensitivity and excellent image-forming property, a novel infrared absorber which can be suitably used in this material and a planographic printing plate including this material.
  • the present inventor has intensively studied for the purpose of improving sensitivity and image-forming property of image-formation materials, and has consequently found that both sensitivity and image-forming property can be improved by using an infrared absorption agent having a specific substituent. Further, the inventor has found a novel infrared absorber that can be suitably used in this agent, leading to completion of the present invention.
  • the image-formation material of the present invention is a heat mode-applicable image-formation material, the image-formation material having: a substrate; and an image-formation layer on the substrate which contains an infrared absorption agent having at least one surface orientation group in a molecule thereof, solubility of the image-formation layer in an alkaline aqueous solution being changeable by action of near-infrared range radiation.
  • the above-mentioned infrared absorption agent is an infrared absorber having at least one surface orientation group selected from fluorine-containing substituents and long chain alkyl groups as described in present claims.
  • the infrared absorber of the present invention is characterized in that it has in the molecule a fluorine-containing substituent having at least 5 fluorine atoms.
  • infrared absorber having such a fluorine substituent there are specifically exemplified infrared absorbers which manifest absorption in the near-infrared range, represented by the following general formulae (1) to (3).
  • R 1 to R 8 each independently represents a hydrogen atom, alkyl group, alkoxy group or halogen atom.
  • R 1 to R 8 may represent a plurality of atoms such that at least one of pairs R 1 and R 3 , R 2 and R 4 , R 5 and R 7 , R 6 and R 8 , R 1 and X 1 , or R 2 and X 2 can be mutually connectable to form an aliphatic 5-membered ring or 6-membered ring, an aromatic 6-membered ring or a substituted aromatic 6-membered ring.
  • R 11 represents an alkyl group.
  • Z 1 represents a heptamethine group, which may have one or more substituents selected from alkyl groups, halogen atoms, amino groups, arylthio groups, alkylthio groups, aryloxy groups, alkoxy groups, barbituric groups and thiobarbituric groups, and which may include a cyclohexene or cyclopentene ring formed by mutually bonding substituents on two methine carbons of the heptamethine group, which ring may further have a substituent selected from alkyl groups and halogen atoms.
  • X - represents a counter ion necessary for neutralizing an electric charge.
  • R F 3 represents a fluorine-containing substituent having at least 5 fluorine atoms.
  • X 3 represents -NH-, -O- or -S-.
  • Each of R 12 and R 13 independently represents an alkyl group. These alkyl groups may have a substituent, and as preferable substituents, aryl groups such as a phenyl group, toluyl group and the like, alkoxy groups such as a methoxy group, ethoxy group, methoxyethoxy group and the like, aryloxy groups such as a phenoxy group, toluyloxy groups and the like, acid groups such as a carboxyl group, sulfonic group and the like or salts thereof, quaternary ammonium groups such as a triethylammonium group, tributylammonium group and the like, a hydroxyl group, amide groups and the like are exemplified.
  • X 1 , X 2 , R 1 to R 8 and X - are as defined for the above-mentioned general formula (1).
  • each of R F 4 , R F 5 , R F 6 and R F 7 independently represents a fluorine-containing substituent having at least 5 fluorine atoms or an alkyl group, and at least one of R F 4 , R F 5 , R F 6 and R F 7 represents a fluorine-containing substituent having at least 5 fluorine atoms.
  • Z 3 represents a pentamethine group, which may have a substituent selected from halogen atoms, hydroxyl groups, alkyl groups, aryl groups and heterocyclic groups.
  • alkyl group and aryl group may further have a substituent, and as preferable further substituents, aryl groups such as a phenyl group, toluyl group and the like, alkoxy groups such as a methoxy group, ethoxy group, methoxyethoxy group and the like, aryloxy groups such as a phenoxy group, toluyloxy groups and the like, are exemplified.
  • this pentamethine group may also contain a cyclohexene or cyclopentene ring formed by mutually bonding substituents on two methine carbons of the pentamethine group, which ring may further have a substituent selected from alkyl groups and halogen atoms.
  • X - represents a counter ion necessary for neutralizing an electric charge.
  • the infrared absorber of the present invention may have a polymethine chain of at least 5 carbon atoms, and an alkyl group of at least 16 carbon atoms, the alkyl group being connected to the polymethine chain via any of nitrogen, oxygen and sulfur and is represented by the following general formula (4):
  • R 14 represents an alkyl group of at least 8 carbon atoms.
  • X 3 represents -NH-, -O- or -S-.
  • R 12 and R 13 independently represents an alkyl group, and may have the same substituents as in the general formula (2).
  • X 1 , X 2 , R 1 to R 8 and X - are as defined for the above-mentioned general formula (1).
  • an infrared absorber which manifests absorption in the near-infrared range and has a surface orientation group as the infrared absorption agent to be used in the image-formation material of the present invention, an infrared absorption agent is localized on the outermost surface (air interface) of a photosensitive layer.
  • diffusion of heat generated near the surface into a substrate is suppressed, and the generated heat is utilized efficiently for forming images. Consequently, an increase in sensitivity can be attained.
  • heat mode-applicable means that recording by heat mode exposure is possible.
  • the definition of the heat mode exposure in the present invention will be explained in detail. As described in Hans-Joachim Timpe, IS&Ts NIP 15: 1999 International Conference on Digital Printing Technologies, P. 209, it is known that there are two modes with respect to a process in which photo-excitation of a light-absorbing substance (for example, dye) in a photosensitive material causes a chemical or physical change to form an image.
  • a light-absorbing substance for example, dye
  • One is a so-called photon mode in which a light-absorbing substance which has been photo-excited is deactivated by a certain photochemical interaction (for example, energy transfer or electron transfer) with another reactive substance in the photosensitive material, and the resulting activated reactive substance causes a chemical or physical change required for the above mentioned image-formation.
  • the other is a so-called heat mode in which a light-absorbing substance that has been photo-excited is deactivated via heat emission, and a reactive substance, by utilizing this heat, causes a chemical or physical change required for the image-formation.
  • photon mode exposure An exposure process utilizing one of the above-mentioned modes is called photon mode exposure or heat mode exposure.
  • a technical difference between the photon mode exposure and the heat mode exposure is whether or not the energy amount of several photons of exposure light can be added and utilized for the energy amount required for the intended reaction. For example, it is hypothesized to use n photons to cause a certain reaction. In photon mode exposure, it is impossible to add the energy amount of photons to each other, due to quantum laws of conservation of energy and momentum, since a photochemical interaction is utilized. That is, to cause some reaction, the relationship: "energy amount of one photon ⁇ energy amount of reaction" must apply.
  • reaction occurs only at an exposure amount of a certain level or more, and an exposure amount of about 50 mJ/cm 2 is usually necessary in view of a relationship with thermal stability of a photosensitive material.
  • problems with low exposure light are avoided.
  • an exposure power density on the surface of a photosensitive material of 5,000 W/cm 2 or more, preferably 10,000 W/cm 2 or more is necessary.
  • Use of a laser with a high power density of 5.0 x 10 5 W/cm 2 or more is not preferable, due to problems such as occurrence of abrasion, staining of a light source, and the like, though this is not described in detail herein.
  • the infrared absorption agent used in the image-formation material of the present invention is an infrared absorption agent having in the molecule thereof at least one surface orientation group as described in present claims.
  • this surface orientation group when a coating solution of an image-formation layer is applied and dried to form the image-formation layer, the infrared absorption agent shifts to places near the surface of the image-formation layer, and is localized.
  • a surface orientation group there are listed functional groups having high hydrophobicity, such as those used as a hydrophobic group of a surfactant.
  • functional groups having high hydrophobicity such as those used as a hydrophobic group of a surfactant.
  • fluorine-containing substituents, and the long chain alkyl groups having 16 or more carbon atoms are described in present claims.
  • These surface orientation groups may be present alone in a molecule, or a plurality of such groups may be present in a molecule.
  • the agent generates heat when irradiated with radiation in the near-infrared range, typically by exposure to infrared light, and recording is conducted by this heat, similarly to a usual infrared absorption agent contained in a recording material which can effect image-formation by exposure in the infrared range. Therefore, it is required that infrared laser light is efficiently converted into heat by the infrared absorption agent localized on the surface of the image-formation layer, and is efficiently used in a reaction for forming images.
  • the infrared absorption agent herein used manifests absorption in the near-infrared range, and specifically, manifests absorption in a wavelength range from 720 nm to 1200 nm, and preferably has an absorption maximum in the wavelength range from 720 nm to 1200 nm.
  • the present inventor has investigated infrared absorbers having a surface orientation group selected from fluorine-containing substituents, long chain alkyl groups and the like, and have found a novel infrared absorber which can be suitably used in the image-formation material of the present invention.
  • This infrared absorber is an infrared absorber having a fluorine-containing substituent having at least 5 fluorine atoms, which is a surface orientation group, or a near-infrared absorber having a polymethine chain that has 5 or more carbon atoms and having an alkyl group that has 16 or more carbon atoms connected to the polymethine chain via any of nitrogen, oxygen and sulfur as described in present claims.
  • the infrared absorber having in the molecule a chromophore which manifests absorption in the near-infrared range as a base skeleton are described in present claims 24 - 27.
  • infrared absorbers having a polymethine chain of the general formulae (1) to (3) are listed as preferable in view of light-heat converting function and stability as an infrared absorber.
  • the near-infrared absorber having a polymethine chain that has 5 or more carbon atoms and having an alkyl group that has 16 or more carbon atoms connected to the polymethine chain via any of nitrogen, oxygen and sulfur will be described.
  • polymethine chain a heptamethine chain, pentamethine chain, nonamethine chain and the like are preferable from the standpoints of stability and absorption wavelength, and a heptamethine chain and pentamethine chain are particularly preferable.
  • infrared absorbers of the general formula (4) are listed in view of light-heat converting function and stability as an infrared absorber.
  • the infrared absorption agent which can be suitably used in the image-formation material of the present invention, the following exemplified compounds (IR-37) to (IR-42) having an alkyl group having 8 or more carbon atoms outside the polymethine chain are also listed.
  • Infrared absorption agents of the above-mentioned general formulae (1) to (4) can be produced by a known organic synthesis technology. Specifically, they can be synthesized by synthetic methods described in USP No. 5,441,866, Zh. Org. Khim. vol. 28 (No. 10) pp. 2156 to 2164 (1992), EP No. 465,543 A1, J. Org. Chem. (Journal of Organic Chemistry) vol. 57 (No. 17) pp. 4578 to 4580 (1992), Japanese Patent Registration No. 2758136, Justus Liebigs Ann. Chem, vol. 623, pp. 204 to 216 (1959), Ukr. Khim. Zh. vol. 22, pp.
  • the infrared absorption agent may be added to an image-formation material, and may then be added together with other components into an image-formation layer. Alternatively, when a layer other than a recording layer is provided, in producing a planographic printing plate, the infrared absorption agent may be added into this layer. These infrared absorption agents may be added alone or in a mixture of two or more.
  • these infrared absorption agents can be added in a ratio of from 0.01 to 50 wt%, preferably from 0.1 to 20 wt%, and more preferably from 0.5 to 15 wt%, based on the total weight of solid components that form the image-formation layer of the image-formation material. If the addition amount is less than 0.01 wt%, the image-forming property thereof will deteriorate, and if added in an amount of over 50 wt%, there is a risk of occurrence of staining at non-image portions in the case of use for a recording layer of a planographic printing plate.
  • pigments black pigments, yellow pigments, orange pigments, brown pigments, red pigments, violet pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and additionally, polymer bond pigments.
  • insoluble azo pigments, azolake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine-based pigments, anthraquinone-based pigments, perylene and perynone-based pigments, thioindigo-based pigments, quinacridone-based pigments, dioxazine-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, dyeing lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.
  • These pigments may be used without surface treatment, or may be surface-treated before use.
  • a method of surface treatment a method of surface coating with a resin or wax, a method of adhering a surfactant, a method of bonding a reactive substance (for example, a silane coupling agent, epoxy compound, polyisocyanate or the like) to the surface of the pigment, and the like are envisaged.
  • a reactive substance for example, a silane coupling agent, epoxy compound, polyisocyanate or the like
  • the particle size of the pigment is preferably from 0.01 ⁇ m to 10 ⁇ m, further preferably from 0.05 ⁇ m to 1 ⁇ m, and particularly preferably from 0.1 ⁇ m to 1 ⁇ m.
  • a particle size of the pigment of less than 0.01 ⁇ m is not preferable from the standpoint of instability of a dispersed substance in a coating solution for an image photosensing layer, and a particle size of over 10 ⁇ m is not preferable from the standpoint of uniformity of the image photosensing layer.
  • dispersing a pigment As a method of dispersing a pigment, known dispersing technologies used in production of ink, production of toners, and the like can be used. As a dispersing machine, an ultrasonic disperser, sand mill, attritor, pearl mill, super mill, ball mill, impeller, disperser, KD mill, colloid mill, Dynatron, triple screw roll mill, press kneader and the like are listed. Details are described in “Saishin Ganryo Oyo Gijutsu” ("Current Pigment Application Technology", published by CMC, 1986).
  • dyes commercially available dyes and, known materials described in the literature such as, for example, "Dye Manual” (edited by Yuki Gosei Kagaku Kyokai, 1960) and the like can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazoloneazo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, diimmonium dyes, aminium dyes and the like are listed.
  • pigments and dyes those which absorb infrared light or near-infrared light are particularly preferable since they are suitable for use with lasers that emit infrared light or near-infrared light.
  • pigments that absorb infrared light or near-infrared light carbon black is suitably used.
  • a dye that absorbs infrared light or near-infrared light for example, cyanine dyes described in JP-A Nos. 58-125246, 59-84356, 59-202829, 60-78787 and the like, methine dyes described in JP-A Nos. 58-173696, 58-181690 and 58-194595 and the like, naphthoquinone dyes described in JP-A Nos.
  • near-infrared absorbing sensitizers described in USP No. 5,156,938 can also be used suitably, and particularly preferably used are arylbenzo(thio)pyrylium salts described in USP No. 3,881,924, trimethinethiapyrylium salts described in JP-A No. 57-142645 (USP No. 4,327,169), pyrylium-based compounds described in JP-A Nos. 58-181051, 58-220143, 59-41363, 59-84248, 59-84249, 59-146063 and 59-146061, cyanine dyes described in JP-A No.
  • near-infrared absorption dyes of formulae (I) and (II) described in USP No. 4,756,993 are listed.
  • the addition amount when added is preferably from about 0.01 to 20 wt% based on the total amount of solid components constituting the image-formation layer.
  • the addition amount is particularly preferably from 0.5 to 10 wt%, and in the case of a pigment, the addition amount is particularly preferably from 0.1 to 5 wt%. If the addition amount of the pigment or dye is less than 0.01 wt%, the effect of addition is not observable, and if over 20 wt%, there is a risk of an undesirable influence on the effect of increased sensitivity that is to be provided by the above-mentioned specific infrared absorption agent.
  • image-formation material of the present invention various known image-formation materials which can be recorded by radiation in the infrared range can be appropriately selected for use.
  • Such recording layers are classified into negative-type layers, in which alkali-developing property is decreased by exposure to infrared light, and positive-type layers, in which developing property increases instead.
  • radical polymerization-based and acid catalyst crosslinking-based (including cation polymerization) recording layers are listed.
  • radical polymerization-based and acid catalyst crosslinking-based layers are particularly preferable from the standpoint of printing endurance.
  • a radical or acid generated by irradiation or heating acts as an initiator or catalyst, and compounds constituting the recording layer cause a polymerization reaction or crosslinking reaction, and cure, forming image portions.
  • positive-type recording layer known positive-type polar-conversion material-based (changing between hydrophobicity and hydrophilicity), acid catalyst decomposition-based and interaction release-based (heat-sensitive positive) recording layers are listed.
  • positive-type polar conversion material-based layers obtained by thermal decomposition of sulfonate esters, and acid catalyst decomposition-based and interaction release-based layers are preferable from the standpoint of image quality.
  • a bond of a polymer compound forming a layer is released or the like, leading to water-solubility or alkaline water-solubility, and such portions can be removed by development to form non-image portions.
  • a polymer compound which is insoluble in water and soluble in an alkaline aqueous solution is preferably contained as a layer constituent component, that is, as a binder.
  • image-formation layers are classified by image formation mechanism and described in detail.
  • the radical polymerization layer which can be used in the image-formation material of the present invention contains a compound that generates a radical due to light or heat (hereinafter, referred to as a radical generator) and a compound which can be radical-polymerized (referred to as a polymerizable compound).
  • a radical is generated from a radical generator in an exposed portion by irradiation with an infrared laser or the like, and this radical acts as an initiator. Consequently, the polymerizable compound is cured by a radical polymerization reaction, to form an image portion.
  • a radical generator and polymerizable compound to be used herein can be appropriately selected for use, providing the strength of a film formed by radical polymerization satisfies the requirements of a recording layer. Further, for improvement of reactivity of the radical generator, promoters such as onium salts, reducing agents and the like can also be used together therewith.
  • promoters such as onium salts, reducing agents and the like can also be used together therewith.
  • components which can be used in a radical polymerization layer for example, compounds described as constituent components of a heat polymerizable recording layer in JP-A No. 8-108621, compounds described as constituent components of a recording layer in JP-A No. 9-34110, and the like can also be preferably used.
  • radical polymerization initiators used in a polymer synthesis reaction for radical polymerization can be usually used without specific restriction.
  • azobisnitrile-based compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobispropionitrile and the like
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, t-butyl perbenzoate, ⁇ -cumyl hydroperoxide, di-t-butyl peroxide, diisopropyl peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, peracids, alkyl peroxy carbamates, nitrosoarylacylamines and the like; inorganic peroxides such as potassium persulfate, ammonium persulfate, potassium perchlorate and the like; azo or diazo-based compounds such as diazo
  • the image-formation material of the present invention When the image-formation material of the present invention is recorded on with an infrared laser, sufficient sensitivity can be obtained even with a radical generator having a large activation energy, since the temperature of the exposed surface may reach as high as 600°C or more, depending on laser energy.
  • the activation energy for generating the radical from the radical generator is preferably 30 kcal/mol or more, and as compounds manifesting such energy, azobisnitrile-based compounds and organic peroxides are listed. Among these, preferable are compounds having excellent stability at ambient temperature, manifesting high decomposing speed in overheating, and becoming colorless in decomposing, and benzoyl peroxide, 2,2'-azobisisobutyronitrile and the like are listed.
  • radical generators may be used alone or in a combination of two or more, and are used in an amount of from about 0.5 to 30 wt%, preferably from 2 to 10 wt% based on the total weight of solid components in a radical polymerization layer.
  • halogen compounds ⁇ -haloacetophenones, trichloromethyltriazines and the like
  • azo compounds aromatic carbonyl compounds (benzoin esters, ketals, acetophonones, o-acyloxyiminoketones, acylphosphine oxides and the like), hexaarylbisimidazole compounds, peroxides and the like are listed, and preferably listed are bisimidazole derivatives disclosed as (A-1) to (A-4) in the above-mentioned JP-A No. 9-34110, page 16.
  • the latter radical generator attains high sensitivity by interaction with an onium salt.
  • an onium salt which can be used together with this radical generator, phosphonium salts, sulfonium salts, iodonium salts and ammonium salts described in the same publication, paragraph Nos. [0022] to [0049] are listed.
  • the amount of the above-mentioned onium salt added is preferably from 0.05 to 50% by weight based on the total weight of solid components in the recording layer, although this may vary depending on the kind and used form of the onium salt.
  • onium salts such as iodonium salts, sulfonium salts, phophonium salts, diazonium salts and the like which can be suitably used as an acid generator in ⁇ Acid crosslinking agents> described later can be used alone as a radical generator without combination with the above-mentioned radical generator, and an addition amount thereof is preferably from 0.05 to 50% by weight based on the total weight of solid components in a recording layer, although this may vary depending on the kind and used form.
  • mono-functional acrylates such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and the like and derivatives thereof, or compounds obtained by substituting acrylate in these compounds with methacrylate, itaconate, crotonate, maleate and the like
  • bifunctional acrylates such as polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, diacrylate of ⁇ -caprolactone adduct of hydroxypivalic acid neopentyl glycol, and the like, and derivatives thereof, or compounds likewise obtained by substituting acrylate in these compounds with methacrylate, and the like
  • polyfunctional acrylates such as trimethylolpropan
  • the polymerizable compounds are selected from monomers and prepolymers having a polymerizable group, including also the above exemplified compounds, and can be used alone, or in a combination of two or more provided there is no problem in compatibility and affinity, according to objectives.
  • a compound having an ethylenically-unsaturated group is contained in an amount preferably from 20 to 80 wt%, more preferably from 30 to 60 wt% in terms of solid components in the radical polymerization layer.
  • a binder resin is used, if necessary.
  • the binder resin polyester-based resins, polyvinylacetal-based resins, polyurethane-based resins, polyamide-based resins, cellulose-based resins, olefin-based resins, vinyl chloride-based resins, (meth)acrylic acid-based resins, styrene-based resins, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polycaprolactone resins, polyacrylonitrile resin, urea resins, epoxy resins, phenoxy resins, rubber-based resins and the like are listed.
  • resins having an unsaturated bond in the resin for example, diallylphthalate resins and derivatives thereof, polypropylene chloride and the like, can be suitably used according to use, because they can be polymerized with the above-mentioned compound having an ethylenically-unsaturated bond.
  • a binder resin one resin selected from the above-mentioned resins, or two or more such resins in combination, can be used.
  • binder resins in an amount of 500 parts by weight or less, more preferably 200 parts by weight or less, for 100 parts by weight of the polymerizable compound.
  • An increase in sensitivity and promotion of the radical polymerization reaction can be realized by adding the above-mentioned specific infrared absorption agent to such a radical polymerization layer.
  • heat polymerization inhibitors are listed. Specific examples thereof include quinone-based and phenol-based compounds such as hydroquinone, pyrogallol, p-methoxyphenol, catechol, ⁇ -naphthol, 2,6-di-t-butyl-p-cresol and the like, and these compounds are used in an amount of 10 parts by weight, preferably from 0.01 to 5 parts by weight for 100 parts by weight of the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder resin.
  • quinone-based and phenol-based compounds such as hydroquinone, pyrogallol, p-methoxyphenol, catechol, ⁇ -naphthol, 2,6-di-t-butyl-p-cresol and the like, and these compounds are used in an amount of 10 parts by weight, preferably from 0.01 to 5 parts by weight for 100 parts by weight of the total amount of the polymerizable compound having an ethy
  • N,N-dialkylaniline derivatives such as compounds described in USP No.4,772,541, column 11, line 58 to column 12, line 35, and the like are listed.
  • plasticizers can be used. Examples include exemplified phthalates, trimellitates, adipates, other saturated or unsaturated carboxylates, citrates, epoxidated soy bean oil, epoxidated linseed oil, stearic epoxys, orthophosphates, phosphates, glycol esters and the like.
  • an additive for generating an acid and promoting decomposition of the radical generator during heating co-use of an acid generator is also preferable.
  • this acid generator those described in detail in explanation of the acid crosslinking layer, described below, can be used.
  • the above-mentioned components can be selected appropriately, dissolved in a suitable solvent, and applied on the substrate to form the radical polymerization layer, and the amount applied is preferably from about 0.01 to 5.0 g/m 2 after drying.
  • an overcoating layer which manifests oxygen impermeability may also be provided adjacent to the radical polymerization layer, for preventing polymerization inhibition by oxygen.
  • water-soluble resins such as polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyvinylpyrrolidone and the like are preferable, and the film thickness thereof is suitably from about 0.2 to 3 ⁇ m.
  • a dye or pigment which does not absorb light from a light source used for recording may be added to the overcoating layer as a filter agent, if necessary.
  • the acid crosslinking layer in the present invention contains a compound which generates an acid due to light or heat (hereinafter, referred to as an acid generator) and a compound which can crosslink using the generated acid as a catalyst (hereinafter, referred to as a crosslinking agent) and, further, a binder polymer which can react with the crosslinking agent in the presence of the acid, for forming the layer containing these compounds.
  • an acid generator a compound which generates an acid due to light or heat
  • a crosslinking agent a compound which can crosslink using the generated acid as a catalyst
  • a binder polymer which can react with the crosslinking agent in the presence of the acid, for forming the layer containing these compounds.
  • the acid crosslinking agent layer having such a property known layers having the same property can be used.
  • layers composed of a radiation-sensitive composition containing a resol resin, novolak resin, latent Br ⁇ nsted acid, and infrared absorption agent.
  • latent Br ⁇ nsted acid indicates a precursor which is decomposed to form a Br ⁇ nsted acid, and is a compound having properties of both the acid generator and the acid crosslinking agent in the present invention.
  • a Br ⁇ nsted acid is believed to catalyze a matrix-formation reaction between a resol resin and a novolak resin.
  • Br ⁇ nsted acids suitable for this purpose trifluoromethanesulfonic acid and hexafluorophosphonic acid are exemplified.
  • ionic latent Br ⁇ nsted acids are preferable. Examples thereof include onium salts, particularly, iodonium, sulfonium, phosphonium, selenonium, diazonium and arsonium salts.
  • Nonionic latent Br ⁇ nsted acids can also be suitably used, and the following compounds: RCH 2 X, RCHX 2 , RCX 3 , R(CH 2 X) 2 and R(CH 2 X) 3 (wherein, X represents Cl, Br, F, CF 3 , or SO 3 , and R represents an aromatic group, an aliphatic group or a bonded body of an aromatic group and an aliphatic group) are listed.
  • a recording layer containing an acid-crosslinkable compound described in JP-A 11-95415 and a binding agent having high molecular weight are also listed as suitable examples.
  • the acid crosslinking layer of the present invention contains an acid generator, crosslinking agent and binder polymer, and other components. Next, these compounds will be illustrated.
  • the compound which generates acid due to light or heat refers to a compound which is decomposed to generate acid by irradiation with infrared light or heating to 100°C or more.
  • a strong acid having a pKa of 2 or less such as sulfonic acid, hydrochloric acid and the like, is preferable.
  • onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and the like are listed. Specifically, compounds described in USP No. 4,708,925 and JP-A No. 7-20629 are listed. Particularly, iodonium salts, sulfonium salts and diazonium salts containing a sulfonate ion as a counter ion are preferable.
  • diazonium salt diazonium compounds described in USP No. 3,867,147, diazonium compounds described in USP No. 2,632,703 and diazo resins described in JP-A Nos.
  • 1-102456 and 1-102457 are also preferable.
  • Benzyl sulfonates described in USP Nos. 5,135,838 and 5,200,544 are also preferable.
  • active sulfonates and disulfonyl compounds described in JP-A Nos. 2-100054, 2-100055 and 8-9444 are also preferable.
  • s-triazines substituted with a halo alkyl, described in JP-A No. 7-271029 are also preferable.
  • These acid generators are added into an acid crosslinking layer in a proportion of from 0.01 to 50% by weight based on the total weight of solid components in the acid crosslinking layer, preferably from 0.1 to 40% by weight, and more preferably from 0.5 to 30% by weight. If the addition amount is less than 0.01% by weight, an image may not be obtained. If the addition amount is over 50% by weight, staining may occur at non-image parts in printing.
  • the crosslinking agent which can be used in the acid crosslinking layer of the present invention is not particularly restricted providing it is a compound which can be crosslinked by action of an acid, and preferably used are phenol derivatives of the following general formula (5) (hereinafter, referred to as a low molecule phenol derivatives, as appropriate), poly-nuclear type phenolic crosslinking agents having in the molecule thereof three or more phenol rings which have two or three hydroxymethyl groups on the rings, of the following general formula (6), and mixtures of the above-mentioned low molecule phenol derivative with the poly-nuclear type phenolic crosslinking agent and/or a resol resin, and the like.
  • phenol derivatives of the following general formula (5) hereinafter, referred to as a low molecule phenol derivatives, as appropriate
  • poly-nuclear type phenolic crosslinking agents having in the molecule thereof three or more phenol rings which have two or three hydroxymethyl groups on the rings
  • (6) mixtures of the
  • Ar 1 represents an aromatic hydrocarbon ring optionally having a substituent.
  • R 1 and R 2 may be the same or different.
  • R 3 represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms.
  • m represents an integer from 2 to 4.
  • n represents an integer from 1 to 3.
  • X represents a divalent connecting group.
  • Y represents a mono-valent to tetra-valent connecting group having the above-mentioned partial structure, or a functional group carrying a hydrogen atom at an end. Z is not present if Y is an end group, or represents a mono-valent to tetra-valent connecting group or functional groups present depending on the number of connecting groups of Y.
  • A represents an r-valent hydrocarbon connecting group having 1 to 20 carbon atoms, and r represents an integer from 3 to 20.
  • p represents an integer from 2 to 3.
  • Phenol derivatives of the general formula (5) are described in detail in Japanese Patent Application No. 11-352210, paragraph nos. [0098] to [0155], submitted by the present applicant.
  • Poly-nuclear type phenolic crosslinking agents having in the molecule three or more phenol rings having 2 or 3 hydroxymethyl groups on the rings, of the general formula (6), are also described in detail in the same specification, in paragraph nos. [0156] to [0165].
  • crosslinking agents may be used alone or in a combination of two or more.
  • the crosslinking agent is used in an addition amount of from 5 to 70% by weight, preferably from 10 to 65% by weight based on the total weight of solid components in the acid crosslinking layer. If the addition amount of the crosslinking agent is less than 5% by weight, the film strength of an image part when an image is recorded will deteriorate, and if over 70% by weight, stability in storage will not be preferable.
  • binder polymer which can be used in the acid crosslinking layer of the present invention
  • polymers having on a side chain or main chain an aromatic hydrocarbon ring to which a hydroxyl group or alkoxy group is directly bonded are listed.
  • alkoxy group those having 20 or less carbon atoms are preferable from the standpoint of sensitivity.
  • aromatic hydrocarbon ring a benzene ring, naphthalene ring or anthracene ring is preferable from the standpoint of availability of raw materials.
  • aromatic hydrocarbon rings may have other substituents than the hydroxyl group or alkoxy group, for example, substituents such as halogen groups, cyano groups and the like.
  • the aromatic hydrocarbon group has no other substituent than the hydroxyl group or alkoxy group.
  • a binder polymer which can be suitably used is a polymer having a constituent unit of the following general formula (7), or a phenol resin such as a novolak resin or the like.
  • Ar 2 represents a benzene ring, naphthalene ring or anthracene ring.
  • R 4 represents a hydrogen atom or methyl group.
  • R 5 represents a hydrogen atom or alkoxy group having 20 or less carbon atoms.
  • X 1 represents a single bond, or a di-valent connecting group having 0 to 20 carbon atoms and containing one or more atoms selected from C, H, N, O and S.
  • k represents an integer from 1 to 4.
  • a homopolymer composed solely of a constituent unit of the general formula (7) may be used as the binder polymer
  • a copolymer having a constituent unit derived from another known monomer together with this specific constituent unit may also be used.
  • the proportion of the constituent unit of the general formula (7) contained in the copolymer obtained therefrom is preferably from 50 to 100% by weight, and further preferably from 60 to 100% by weight.
  • the polymer used in the present invention has a weight-average molecular weight of preferably 5,000 or more, further preferably from 10,000 to 300,000, and a number-average molecular weight of preferably 1,000 or more, further preferably from 2,000 to 250,000.
  • the degree of polydispersity is preferably 1 or more, and further preferably from 1.1 to 10.
  • These polymers may be any of a random polymer, block polymer, graft polymer and the like, and a random polymer is preferable.
  • novolaks As a novolak resin suitably used in the present invention, phenol novolaks, o-, m- and p-cresol novolaks, and copolymers thereof, and novolaks obtained by utilizing phenols substituted with a halogen atom, alkyl group or the like, are listed.
  • the novolak resin has a weight-average molecular weight of preferably 1,000 or more, further preferably from 2,000 to 20,000, and a number-average molecular weight of preferably 1,000 or more, further preferably from 2,000 to 15,000.
  • the degree of polydispersity is preferably 1 or more, and further preferably from 1.1 to 10.
  • the heterocyclic ring means a ring containing one or more heteroatoms other than carbon, as atoms constituting the ring system.
  • heteroatoms used nitrogen atoms, oxygen atoms, sulfur atoms and silicon atoms are preferable. It is believed that by use of a polymer having such a heterocyclic group, a reaction tends to occur chemical-structurally, due to function of a lone pair existing in this heterocyclic ring, to thereby form a film having excellent printing endurance.
  • the binder polymer as described above used in the present invention may be used alone or in a combination of two or more.
  • This polymer is added in a proportion of from 20 to 95% by weight based on the total weight of solid components in an acid crosslinking layer, and preferably from 40 to 90% by weight. If the addition amount is less than 20% by weight, strength of image parts will be deficient when images are formed. On the other hand, if the addition amount is over 95% by weight, images will not be formed.
  • this acid crosslinking layer sensitivity can be improved by inclusion of the infrared absorption agent.
  • this acid crosslinking layer various additives such as a surfactant and the like can be used therewith for purposes of improving applicability and film quality and the like.
  • interaction releasing systems heat sensitive positive
  • acid catalyst decomposition systems acid catalyst decomposition systems
  • polarity-conversion systems are listed. These are described below in this order.
  • the interaction releasing system is constituted of a water-insoluble polymer, an alkaline water-soluble polymer, and an infrared absorption agent.
  • the alkali-soluble polymer compound which can be used in a positive recording layer includes homopolymers containing an acidic group on the main chain and/or side chain of the polymer, copolymers thereof, and mixtures thereof.
  • those having an acidic group exemplified in the following (1) to (6) on the main chain and/or side chain of the polymer are preferable from the standpoint of solubility in an alkaline developing solution, and from the standpoint of manifestation of dissolution-suppressing ability.
  • Ar represents a di-valent aryl connecting group optionally having a substituent
  • R represents a hydrocarbon group optionally having a substituent
  • alkaline water-soluble polymers having an acidic group selected from the above-mentioned (1) to (6) alkaline water-soluble polymers having (1) a phenol group, (2) a sulfonamide group and (3) an active imide group are most preferable from the standpoints of solubility in the alkaline developing solution, developing latitude, and sufficient ensuring of film strength.
  • alkaline water-soluble polymers having an acidic group selected from the above-mentioned (1) to (6) the following polymers are exemplified.
  • novolak resins such as polycondensates of phenol with formaldehyde; polycondensates of m-cresol with formaldehyde; polycondensates of p-cresol with formaldehyde; polycondensates of m-/p-mixed cresol with formaldehyde; polycondensates of phenol, cresol (may be m-, p- or m-/p- mixed type) and formaldehyde, and the like; and polycondensates of pyrogallol with acetone are listed. Further, copolymers obtained by copolymerizing a compound having a phenol group on the side chain are listed. Alternatively, copolymers obtained by copolymerizing a compound having a phenol group on the side chain can also be used.
  • acrylamides As the compound having a phenol group, acrylamides, methacrylamides, acrylates, methacrylates, hydroxystyrenes and the like are listed.
  • the alkaline water-soluble polymer preferably has a weight-average molecular weight from 5.0 ⁇ 10 2 to 2.0 ⁇ 10 4 and a number-average molecular weight from 2.0 ⁇ 10 2 to 1.0 ⁇ 10 4 , from the standpoint of image-formation property.
  • These polymers may be used alone, or in a combination of two or more.
  • a polycondensate of phenol with formaldehyde having as a substituent an alkyl group having 3 to 8 carbon atoms such as a polycondensate of t-butylphenol with formaldehyde and a polycondensate of octylphenol with formaldehyde as described in USP No. 4123279
  • alkaline water-soluble polymers having a phenol structure having an electron attractive group on an aromatic ring as described in Japanese Patent Application No. 11-47019 submitted previously by the present inventor, and the like may be used together.
  • alkaline water-soluble polymer having a sulfonamide group for example, polymers constituted, as the main constituent component, of a minimum constituent unit derived from a compound having a sulfonamide group are listed.
  • compounds having in the molecule one or more sulfonamide groups in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated bonds are listed.
  • low molecular weight compounds having in the molecule an acryloyl group, allyl group or vinyloxy group and a substituted or mono-substituted aminosulfonyl group or a substituted sulfonylimino group are preferable.
  • compounds of the following general formulae 8 to 12 are listed.
  • each of X 1a and X 2a independently represents -O- or -NR 27 -.
  • Each of R 21 and R 24 independently represents a hydrogen atom or -CH 3 .
  • Each of R 22 , R 25 , R 29 , R 32 and R 36 independently represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group, having 1 to 12 carbon atoms and optionally having a substituent.
  • Each of R 23 , R 27 and R 33 independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, having 1 to 12 carbon atoms and optionally having a substituent.
  • each of R 26 and R 37 independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, having 1 to 12 carbon atoms and optionally having a substituent.
  • Each of R 28 , R 30 and R 34 independently represents a hydrogen atom or -CH 3 .
  • Each of R 31 and R 35 independently represents a single bond, or an alkyl group, a cycloalkylene group, an arylene group or an aralkylene group, having 1 to 12 carbon atoms and optionally having a substituent.
  • Each of Y 3 and Y 4 independently represents a single bond, or -CO-.
  • m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide, N-(p-aminosulfonylphenyl)acrylamide and the like can be suitably used in the positive planographic printing material of the present invention.
  • alkaline water-soluble polymer having an active imide group for example, polymers constituted, as the main constituent component, of a minimum constituent unit derived from a compound having an active imide group are listed.
  • compounds having in the molecule one or more active imide groups of the following structural formula and one or more polymerizable unsaturated bonds are listed.
  • N-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl)acrylamide and the like can be suitably used.
  • alkaline water-soluble polymer having a carboxyl group for example, polymers constituted, as the main constituent component, of a minimum constituent unit derived from a compound having in the molecule one or more carboxyl groups and one or more polymerizable unsaturated groups are listed.
  • alkaline water-soluble polymer having a sulfonic group for example, polymers constituted, as the main constituent component, of a minimum constituent unit derived from a compound having, in the molecule, one or more sulfonic groups and one or more polymerizable unsaturated groups are listed.
  • alkaline water-soluble polymer having a phosphate group for example, polymers constituted, as the main constituent component, of a minimum constituent unit derived from a compound having in the molecule one or more phosphate groups and one or more polymerizable unsaturated groups are listed.
  • the minimum constituent unit having an acidic group selected from the above-mentioned (1) to (6) constituting an alkaline water-soluble polymer to be used in the positive recording layer is not necessarily restricted to one kind specifically, and those obtained by copolymerizing two or more minimum constituent units having the same acidic group or two or more minimum constituent units having different acidic groups can also be used.
  • compounds having an acidic group selected from (1) to (6) to be copolymerized are contained in the copolymer preferably in an amount of 10 mol% or more, and more preferably 20 mol% or more. If less than 10 mol%, there is a tendency that developing latitude can not be sufficiently improved.
  • a chemical amplification layer is preferably formed on an exposure surface of an uppermost layer of the recording layer, and contains, as an essential component, a compound which generates acid due to action of light or heat (acid generator), and a compound which manifests cleavage of a chemical bond using the generated acid as a catalyst, to increase solubility in the alkaline developing solution (an acid-decomposable compound).
  • the chemical amplification layer may further contain a polymer compound which is a binder component for forming this layer, or the above-mentioned acid-decomposable compound itself may be a polymer compound which performs the function of a binder component, or a precursor thereof.
  • the compound which manifests cleavage of a chemical bond using the acid as a catalyst to increase solubility in the . alkaline developing solution is, in other words, a compound having in the molecule a bonding group which can be decomposed by an acid.
  • a compound having in the molecule a bonding group which can be decomposed by an acid those described as "(b) compound having at least one bond decomposable by an acid" in JP-A No. 9-171254 can be used.
  • the bond decomposable by an acid for example, -(CH 2 CH 2 O) n - groups (n represents an integer from 2 to 5) and the like are preferably listed.
  • compounds of the following general formula (13) are preferably used from the standpoints of sensitivity and developing property.
  • each of R, R 1 and R 2 represents a hydrogen atom, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, sulfo group, carboxyl group or hydroxyl group; each of p, q and r represents an integer from 1 to 3; and each of m and n represents an integer from 1 to 5.
  • alkyl groups represented by R, R 1 and R 2 may be linear or branched, and examples thereof include an ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group and the like.
  • alkoxy groups for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, pentoxy group and the like are listed.
  • Sulfo groups and carboxyl groups include salts thereof.
  • compounds of the general formula (13) those in which m and n are 1 or 2 are particularly preferable.
  • Compounds of the general formula (13) can be synthesized by a known method.
  • an acid-decomposable compound which can be used with the present invention there are listed compounds having a C-O-C bond described in JP-A Nos. 48-89603, 51-120714, 53-133429, 55-12995, 55-126236 and 56-17345; compounds having a Si-O-C bond described in JP-A Nos. 60-37549 and 60-121446; and other acid-decomposable compounds described in JP-A Nos. 60-3625 and 60-10247. Further listed are compounds having a Si-N bond described in JP-A No. 62-222246, carbonates described in JP-A No. 62-251743, orthocarbonates described in JP-A No.
  • JP-A No. 62-244038 orthotitanates described in JP-A No. 62-280841, orthosilicates described in JP-A No. 62-280842, acetals, ketals and orthocarbonates described in JP-A Nos. 63-010153, 9-171254, 10-55067, 10-111564, 10-87733, 10-153853, 10-228102, 10-268507, 10-282648 and 10-282670, EP-0884547A1, and compounds having a C-S bond described in JP-A No. 62-244038.
  • acid-decomposable compounds particularly compounds having a C-O-C bond, compounds having a Si-O-C bond, orthocarbonates, acetals, ketals and silyl ethers described in JP-A Nos. 53-133429, 56-17345, 60-121446, 60-37549, 62-209451, 63-010153, 9-171254, 10-55067, 10-111564, 10-87733, 10-153853, 10-228102, 10-268507, 10-282648 and 10-282670, and EP-0884547A1 are preferable.
  • polymer compounds which have in the main chain a repeating acetal or ketal part and of which solubility in an alkaline developing solution is increased by the generated acid are preferably used.
  • These acid-decomposable compounds may be used alone or in a combination of two or more.
  • these compounds are added into the chemical amplification layer in a proportion of from 5 to 70% by weight based on the total weight of solid components in the layer, preferably from 10 to 50% by weight, and more preferably from 15 to 35% by weight. If the addition amount is less than 5% by weight, staining of non-image parts tends to occur, and if over 70% by weight, film strength in image parts becomes insufficient. That is, both these cases are not preferable.
  • a polarity-conversion material which changes from lipophilic to hydrophilic when heated is a material which varies from a state in which affinity, such as swelling or dissolution or the like, is not manifested for water at normal temperature to a state in which affinity is manifested for water.
  • This variation may be or may not be accompanied by a chemical reaction.
  • a variation accompanied by a chemical reaction is preferable since the extent of conversion of polarity is large.
  • a polarity-conversion reaction a reaction that generates a hydrophilic group by heat is exemplified.
  • hydrophilic substituent As a hydrophilic substituent, acidic groups such as a phosphonic group, sulfonic group, carboxyl group, sulfonamide, phenol and the like, a hydroxyl group, amino groups and the like, and onium salts such as an ammonium salt and the like are listed. Reactions are preferable in which such a substituent is manifested by action of heat.
  • a polarity-conversion material carboxylates described in JP-A No. 7-186562, photochromic compounds described in JP-A Nos. 9-240148, 4-44895, 8-3463 and 8-156401, inorganic compounds described in JP-A No.
  • protective groups that generate the above-mentioned hydrophilic group are also used suitably.
  • protective groups those described in "Protective Groups in Organic Synthesis” (Greene, Theodra W. and Wuts, Peter G.M., Wiley-Interscience Publication), and "Protecting Groups” (Philip J. Kocienski, George Thieme Verlag Stuttgart) are listed. These may have high molecular weight or low molecular weight.
  • the reaction temperature is preferably from 80°C to 300°C, particularly preferably from 120°C to 200°C. When the reaction temperature is lower, storage stability lowers, and when the reaction temperature is higher, sensitivity lowers.
  • various additives can be further added, if necessary.
  • addition of other onium salts, aromatic sulfone compounds, aromatic sulfonate compounds, poly-functional amine compounds and the like is preferable since a function to inhibit dissolution of an alkaline water-soluble polymer into a developing solution can be improved when such compounds are added.
  • onium salts diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like are listed.
  • the onium salt is preferably added in an amount of from 1 to 50% by weight based on the total amount of solid components constituting the image-formation material, more preferably from 5 to 30% by weight, and particularly preferably from 10 to 30% by weight.
  • cyclic acid anhydrides, phenols, and organic acids can be used together therewith.
  • a cyclic acid anhydride phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy- ⁇ 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like described in USP No. 4,115,128 can be used.
  • phenol bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-trihydroxybenzophenone, 4,4',4"-trihydroxytriphenylmethane, 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane and the like are listed.
  • organic acid sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates and carboxylic acids and the like described in JP-A Nos. 60-88942 and 2-96755 and the like are listed.
  • the proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids present in the image-formation material is preferably from 0.05 to 20% by weight, more preferably from 0.1 to 15% by weight, and particularly preferably from 0.1 to 10% by weight.
  • epoxy compounds, vinyl ethers, phenol compounds having a hydroxymethyl group and phenol compounds having an alkoxy methyl group described in JP-A No. 8-276558, and crosslinkable compounds having an alkali disolution-suppressing action described in JP-A No. 11-160860, submitted previously by the present inventor, and the like can be appropriately added, according to objectives.
  • nonionic surfactants as described in JP-A Nos. 62-251740 and 3-208514, and ampholytic surfactants as described in JP-A Nos. 59-0121044 and 4-13149 can be added for widening processing stability under developing conditions.
  • a printout agent for obtaining a visible image directly after heating by exposure and a dye or pigment as an image coloring agent can be added.
  • a trihalomethyl group oxazole-based compounds and triazine-based compounds are exemplified, and both of these are excellent in stability with the lapse of time, and give a clear printout image.
  • Oil-soluble dyes and basic dyes are listed as suitable dyes, including salt-forming organic dyes. Specifically, Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (these are manufactured by Orient Chemical Industry Co.), Victoria Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015) and the like are listed. Dyes described in JP-A No. 62-293247 are particularly preferable. These dyes can be added to a printing material in a proportion of from 0.01 to 10% by weight based on the total amount of solid components in the printing material, and preferably from 0.1 to 3% by weight.
  • a plasticizer may be added to the printing plate material of the present invention, for imparting flexibility of a film and the like, if necessary.
  • a plasticizer may be added to the printing plate material of the present invention, for imparting flexibility of a film and the like, if necessary.
  • a recording layer coating solution containing the image-formation material of the present invention, or coating solution components of a desired layer such as a protective layer or the like, can be dissolved in a solvent and applied to a suitable substrate, to produce an image-formation material.
  • the solvent herein used include, but are not limited to, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetoamide, N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, ⁇ -butyrolactone, toluene, water and the like.
  • the concentration of the above-mentioned components (all solid components including additive) in the solvent is preferably from 1 to 50% by weight.
  • the coating amount after drying (solid component) on the substrate differs depending on use, and is preferably from 0.5 to 5.0 g/m 2 , in general, for a photosensitive printing plate.
  • the coating method various methods can be used. For example, bar coater coating, rotation coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating and the like are listed. When the coating amount decreases, apparent sensitivity increases but the film property of the recording layer decreases.
  • Surfactants for improving coatability for example, fluorine-based surfactants as described in JP-A No. 62-170950, can be added to the recording layer coating solution using the image-formation material in the present invention.
  • a preferable addition amount is from 0.01 to 1% by weight, further preferably from 0.05 to 0.5% by weight, based on the whole printing plate material.
  • the substrate used for the image-formation material of the present invention is a dimensionally stable plate, and examples thereof include paper, paper laminated with a plastic (e.g., polyethylene, polypropylene, polystyrene and the like), metal plates (e.g., aluminum, zinc, copper and the like), plastic films (e.g., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like), paper laminated or deposited with metals as described above, and plastic films and the like.
  • a plastic e.g., polyethylene, polypropylene, polystyrene and the like
  • metal plates e.g., aluminum, zinc, copper and the like
  • plastic films e.g., cellulose diacetate, cellulose triacetate, cellulose propionat
  • polyester films and aluminum plates are preferable.
  • an aluminum plate which has excellent dimension stability and is relatively cheap, is particularly preferable.
  • a suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as the main component and containing trace amounts of hetero elements. Further, a plastic film laminated or deposited with aluminum may be permissible.
  • the hetero elements contained in the aluminum alloy silicon, iron, manganese, copper, magnesium, chromium, bismuth, nickel, titanium and the like are listed. The content of hetero elements in the alloy is at most 10% by weight.
  • a particularly suitable aluminum in the present invention is pure aluminum. However, since completely pure aluminum is difficult to produce from the refining technology standpoint, trace amounts of hetero elements may be contained.
  • the aluminum plate applied to the present invention is not specified regarding composition, and aluminum plates made of conventionally known and used raw materials can be utilized appropriately.
  • the aluminum plate used in the present invention has a thickness of about from 0.1 mm to 0.6 mm, preferably from 0.15 mm to 0.4 mm, and particularly preferably from 0.2 mm to 0.3 mm.
  • a degreasing treatment Prior to roughening of the aluminum plate, there is conducted a degreasing treatment with, for example, a surfactant, organic solvent, alkaline aqueous solution or the like, for removing a rolling oil from the surface, if necessary.
  • a surfactant for example, organic solvent, alkaline aqueous solution or the like
  • the treatment for roughening the surface of the aluminum plate may be conducted by various methods and may be, for example, effected by a method of mechanical roughening, a method of dissolving and roughening the surface electrochemically, or a method of selectively dissolving the surface chemically.
  • a method of mechanical roughening known methods such as a ball polishing method, brush polishing method, blast polishing method, buff polishing method or the like can be used.
  • the electrochemical roughening method there are methods conducted by alternating current or direct current in hydrochloric acid or nitric acid electrolytes. Further, a method obtained by combining both of these can also be utilized, as disclosed in JP-A No. 54-63902.
  • An aluminum plate thus surface-roughened is subjected to an alkali etching treatment and neutralization treatment if necessary, and then subjected to an anodizing treatment for enhancing water-retaining property and abrasion resistance of the surface, if desired.
  • anodizing treatment for enhancing water-retaining property and abrasion resistance of the surface, if desired.
  • the electrolyte used in the anodizing treatment of the aluminum plate use of various electrolytes for forming a porous oxide film is possible. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately selected depending on the kind of electrolyte.
  • Treatment conditions of anodizing cannot be generally specified since they change variously depending on electrolytes used. However, in general, it is appropriate that concentration of electrolytes is from 1 to 80% by weight, liquid temperature is from 5 to 70°C, current density is from 5 to 60 A/dm 2 , voltage is from 1 to 100 V, and electrolysis time is from 10 seconds to 5 minutes.
  • a hydrophilization treatment is performed on the surface of the aluminum, if necessary.
  • the hydrophilization treatment used in the present invention there is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in USP Nos. 2,714,066, 3,181, 461, 3,280,734 and 3,902,734.
  • the substrate is immersed in a sodium silicate aqueous solution, or electrolyzed.
  • potassium zirconate fluoride disclosed in JP-B No. 36-22063, or polyvinyl phosphonic acid as disclosed in USP Nos. 3,276,868, 4,153,461 and 4,689,272.
  • the image-formation material of the present invention comprises a substrate carrying thereon a recording layer provided with the image-formation layer of the present invention. If necessary, a primer layer can be provided therebetween.
  • various organic compounds can be used and, for example, selected from carboxymethylcellulose, dextrin, gum Arabic; phosphonic acids having an amino group such as 2-aminoethylphosphonic acid and the like; organic phosphonic acids such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid, ethylene diphosphonic acid and the like optionally having a substituent; organic phosphoric acid such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, glycerophosphoric acid and the like optionally having a substituent; organic phosphinic acids such as phenylphosphinic acid, naphthylhphosphinic acid, alkylphosphinic acid, glycerophosphinic acid and the like optionally having a substituent; amino acids such as glycine, ⁇ -alanine and the like; and hydroch
  • solid lasers and semiconductor lasers radiating infrared light having wavelengths from 720 to 1200 nm and the like are listed.
  • light sources having emitting wavelengths from the near-infrared range to the infrared range are preferable, and solid lasers and semiconductor lasers are particularly preferable.
  • alkaline aqueous solutions can be used.
  • inorganic alkali salts are listed, such as sodium silicate, potassium silicate, sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide, lithium hydroxide and the like.
  • organic alkali agents are also used such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like.
  • alkali agents are used alone or in a combination of two or more.
  • Particularly preferable developing solutions among these alkali agents are silicate aqueous solutions of sodium silicate, potassium silicate and the like.
  • the reason for this is that developing property can be controlled by the concentrations and the ratio of silicon oxide SiO 2 , which is a component of a silicate, to an alkali metal oxide M 2 O.
  • Alkali metal silicates as described in JP-A No. 54-62004 and JP-B No. 57-7427 are effectively used.
  • a large number of photosensitive plates can be treated without changing the developing solution in a developing tank for a long period of time, by adding an aqueous solution (replenishment solution) having higher alkali strength than the developing solution to the developing solution.
  • This replenishment method is also preferably applied in this invention.
  • Various surfactants and organic solvents can be added to the developing solution and replenishment solution, if necessary, for purposes of enhancing promotion/suppression of the developing solution, dispersion of development residue and ink-affinity of image parts of the printing plate.
  • preferable surfactants anionic, cationic, nonionic and ampholytic surfactants are listed.
  • Reducing agents can also be added to the developing solution and replenishment solution as necessary, such as hydroquinone, resorcin, and sodium salts and potassium salts and the like of inorganic acids such as sulfurous acid, hydrogensulfurous acid and the like. Further, organic carboxylic acids, defoaming agents and hard water softening agents can also be added, if necessary.
  • the printing plate subjected to development treatment using the above-mentioned developing solution and replenishment solution is subjected to post-treatment with a washing solution, a rinse solution containing surfactants and the like, or a de-sensitizing solution containing gum Arabic and a starch derivative.
  • a post-treatment when the image-formation material of the present invention is used for a printing plate these treatments can be variously combined and used.
  • automatic developing machines for printing plates have been widely used for rationalization and standardization of plate production work in plate production and printing industries.
  • These automatic developing machines are, in general, composed of a development section and a post-treatment section, and have an apparatus for transporting a printing plate, treating solution vessels, and a spray apparatus.
  • a developing treatment therein is conducted by spraying treating solutions sucked up by pumps through spray nozzles while horizontally transporting a printing plate which has been exposed.
  • a method in which a printing plate is treated by being immersed and transported by a submerged guide roll in a treating solution vessel filled with a treatment solution.
  • treatment can also be conducted while replenishing a replenishment solution to the treatment solution based on treatment amount, working time and the like.
  • a photosensitive planographic printing plate using the image-formation material of the present invention will be described.
  • a planographic printing plate obtained by image-wise exposure, development, water-washing and/or rinse and/or gum-drawing carries unnecessary image parts (for example, a film edge trace of an original picture film and the like), the unnecessary image parts should be eliminated.
  • a method for example, as described in JP-B No. 2-13293, in which an elimination solution is applied to the unnecessary image parts, left as is for a given time, and then washed with water is preferably used.
  • a method can also be used, as described in JP-A No. 59-174842, in which an active beam introduced through an optical fiber is allowed to irradiate the unnecessary image parts before development.
  • planographic printing plate obtained as described above can be, after application of desensitizing gum as necessary, subjected to a printing process. If a planograhpic printing plate having higher printing endurance is desired, a burning treatment is performed.
  • the amount of the surface smoothing solution applied is, in general, suitably from 0.03 to 0.8 g/m 2 (dry weight).
  • the planographic printing plate onto which the surface smoothing agent has been applied is dried if necessary, and then heated to a high temperature by a burning processor (for example, a burning processor: "BP-1300", available from Fuji Photo Film Co., Ltd.) or the like.
  • a burning processor for example, a burning processor: "BP-1300", available from Fuji Photo Film Co., Ltd.
  • the heating temperature is from 180 to 300°C and the heating time is from 1 to 20 minutes, depending on the kinds of image-forming components.
  • planographic printing plate obtained by such treatments is subjected to treatment in an offset printing machine, and used for printing a large number of sheets.
  • Example 1 example of a positive image-formation material
  • An aluminum plate (material 1050) having a thickness of 0.3 mm was degreased by washing with trichloroethylene. Then, the surface thereof was grained using a nylon brush and a pumice-water suspension of 400 mesh, and washed thoroughly with water. This plate was immersed in a 25% aqueous sodium hydroxide solution at 45°C for 9 seconds to effect etching, and washed with water, then further immersed in a 20% nitric acid solution for 20 seconds, and washed with water. The etched amount of the grained surface in this procedure was about 3 g/m 2 .
  • the plate was treated with a current density of 15 A/dm 3 using 7% sulfuric acid as an electrolyte, to form thereon a direct current anodized film of 3 g/m 2 .
  • the plate was washed with water and dried, a primer solution described below was applied thereto, and the film was dried at 90°C for 1 minute. The amount of the film applied after drying was 10 mg/m 2 .
  • the following photosensitive layer coating solution [A] was applied to give a coating amount of 1.8 g/m 2 , to obtain a planographic printing plate [A-1].
  • Planographic printing plates [A-2] and [A-3] were obtained in the same manner as in Example 1 except that the infrared absorption agent compounded in the photosensitive layer coating solution [A] in Example 1 was replaced with the exemplary compounds described in the following table 1.
  • a planographic printing plate [A-C] was obtained in the same manner as in Example 1 except that the infrared absorption agent compounded in the photosensitive layer coating solution [A] in Example 1 was replaced with IR-792 perchlorate (manufactured by Sigma Aldrich Japan K.K.) having the following structure.
  • the following photosensitive layer coating solution [B] was applied to a substrate obtained in the same manner as in Example 1 such that a coating amount was 1.6 g/m 2 , to obtain a planographic printing plate [B-1].
  • Planographic printing plates [B-2] and [B-3] were obtained in the same manner as in Example 4 except that the infrared absorption agent compounded in the photosensitive layer coating solution [B] in Example 4 was replaced with the exemplary compounds described in the following table 1.
  • a planographic printing plate [B-C] was obtained in the same manner as in Example 4 except that the infrared absorption agent compounded in the photosensitive layer coating solution [B] in Example 4 was replaced with IR-792 perchlorate (manufactured by Sigma Aldrich Japan K.K.).
  • the obtained planographic printing plates were exposed using a semiconductor laser having an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 ⁇ m (1/e 2 ) at a main scanning rate of 5 m/sec. Then, development was conducted using an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.; trade name: PS Processor 900 VR) charged with a developing solution DP-4 and a rinse liquid FR-3 (1:7), both manufactured by Fuji Photo Film Co., Ltd. In this procedure, DP-4 was diluted with water at 1:8. Line widths of non-image parts obtained using this developing solution were measured, and an irradiation energy of the laser that corresponded to these line width was calculated as sensitivity. Values of measured sensitivity are shown in Table 1.
  • a photosensitive layer coating solution [C] having the above-mentioned composition the kind of infrared absorption agent was changed as shown in Table 2, to obtain four kinds of coating solution [C-1] to [C-4]. These solutions were applied in the same manner as in Example 1, and dried at 100°C for 1 minute, to obtain negative planographic printing plates [C-1] to [C-4] as Examples 7 to 10. The coating weight after drying was 1.3 g/m 2 .
  • the obtained negative planographic printing plates [C-1] to [C-4] were exposed with a semiconductor laser emitting infrared light having a wavelength of 830 nm, the same as in Example 1. After exposure, the plates were heated for 1 minute in an oven at 140°C, and then passed through an automatic developing machine charged with the developing solution DP-4 (1:4) and rinse liquid FR-3 (1:7), manufactured by Fuji Photo Film Co., Ltd. In each case, an excellent negative image was obtained.
  • a negative planographic printing plate [C-C] (Comparative Example 3) was obtained in the same manner as in Examples 7 to 10, except that the infrared absorption agents used in Examples 7 to 10 were replaced with IR-792 perchlorate in the photosensitive layer coating solution [C].
  • the obtained planographic printing plate [C-C] was subjected to exposure, heat treatment and development in the same manner as for Examples 7 to 10, and sensitivity was measured in the same manner as for Examples 1 to 6. The results are shown in Table 2.
  • a planographic printing plate using the infrared absorption agent of the present invention has higher sensitivity and more excellent image-forming property as compared with a known infrared absorption agent.
  • a photosensitive layer coating solution [D] having the above-mentioned composition the kind of infrared absorption agent was changed as shown in Table 3 to obtain two kinds of coating solution, [D-1] and [D-2]. These solutions were applied on to a substrate in the same manner as for Example 1, and dried at 115°C for 45 seconds, to obtain negative planographic printing plates [D-1] and [D-2] as Examples 11 and 12. The coating weight after drying was 1.4 g/m 2 .
  • the obtained negative planographic printing plates [D-1] and [D-2] were exposed with a semiconductor laser emitting infrared light having a wavelength of 830 nm, the same as in Examples 1 to 10, and then passed through an automatic developing machine charged with DN-3C (1:2), a developing solution manufactured by Fuji Photo Film Co., Ltd., and the rinse liquid FR-3 (1:7). In both cases, an excellent negative image was obtained.
  • a negative planographic printing plate [D-C] (Comparative Example 4) was obtained in the same manner as in Examples 11 to 12 except that the infrared absorption agent in the photosensitive layer coating solution [D] used in Examples 11 to 12 was replaced with IR-786 perchlorate (manufactured by Sigma Aldrich Japan K.K.),.
  • the obtained planographic printing plate [D-C] was subjected to exposure, heat treatment and development in the same manner as for Examples 11 to 12, and sensitivity was measured in the same manner as for Examples 1 to 10. The results are shown in Table 3.
  • the present invention can provide an image-formation material having high sensitivity and also excellent image-forming property, by use of the above-described specific infrared absorption agent.
  • a planographic printing plate using this image-formation material can perform direct plate production with an infrared laser, and has high sensitivity and excellent image-forming property.
  • the image-formation material of the present invention shows high sensitivity to an infrared laser and excellent image formation property. Further, a planographic printing plate using this image-formation material provides effects such that direct plate production is possible with an infrared laser, sensitivity is high and image formation property is excellent.

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Claims (31)

  1. Matériau de formation d'image applicable en mode thermique comprenant :
    un substrat ; et
    une couche de formation d'image sur le substrat qui contient un agent absorbeur d'infrarouge, la solubilité de ladite couche de formation d'image dans une solution aqueuse alcaline étant susceptible d'être changée par l'action d'un rayonnement dans la gamme proche infrarouge,
    dans lequel l'agent absorbeur d'infrarouge comprend une chaíne polyméthine d'au moins 5 atomes de carbone et un groupe alkyle d'au moins 16 atomes de carbone, ledit groupe alkyle étant lié à la chaíne polyméthine via l'un quelconque parmi l'azote, l'oxygène et le soufre, et
    dans lequel l'agent absorbeur d'infrarouge est représenté par la formule générale (4) comme suit :
    Figure 01120001
    dans laquelle formule : R14 représente un groupe alkyle d'au moins 16 atomes de carbone ; X3 représente -NH-, -O- ou -S- ; chacun de R12 et R13 représente indépendamment un groupe alkyle ; chacun de X1 et X2 représente indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique ; et
    Z2 étant une chaíne polyméthine d'au moins 5 atomes de carbone.
  2. Matériau de formation d'image applicable en mode thermique comprenant :
    un substrat ; et
    une couche de formation d'image sur le substrat qui contient un agent absorbeur d'infrarouge, la solubilité de ladite couche de formation d'image dans une solution aqueuse alcaline étant susceptible d'être changée par l'action d'un rayonnement dans la gamme proche infrarouge,
    dans lequel l'agent absorbeur d'infrarouge comprend un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16.
  3. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ledit agent absorbeur d'infrarouge a une absorption à une longueur d'onde de 720 nm à 1200 nm.
  4. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ledit agent absorbeur d'infrarouge est contenu en une quantité de 0,01 à 50 % en poids par rapport aux matières solides totales de ladite couche de formation d'image.
  5. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ladite couche de formation d'image est une couche de formation d'image du type positif.
  6. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ladite couche de formation d'image est une couche de formation d'image du type négatif.
  7. Matériau de formation d'image selon la revendication 5, dans lequel ladite couche de formation d'image comprend un polymère insoluble dans l'eau, un polymère soluble dans l'eau alcaline, et l'agent absorbeur d'infrarouge.
  8. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ladite couche de formation d'image comprend une couche de polymérisation radicalaire contenant un générateur de radicaux et un composé polymérisable.
  9. Matériau de formation d'image selon la revendication 8, dans lequel ledit générateur de radicaux est contenu en une quantité de 0,5 à 30 % en poids par rapport aux matières solides totales de ladite couche de polymérisation radicalaire.
  10. Matériau de formation d'image selon la revendication 8, dans lequel ledit composé polymérisable a dans une molécule de celui-ci au moins deux groupes acryliques ou méthacryliques.
  11. Matériau de formation d'image selon la revendication 7, dans lequel ladite couche de formation d'image comprend une couche de polymérisation radicalaire contenant un générateur de radicaux et un composé polymérisable.
  12. Matériau de formation d'image selon la revendication 11, dans lequel ledit générateur de radicaux est contenu en une quantité de 0,5 à 30 % en poids par rapport aux matières solides totales de ladite couche de polymérisation radicalaire.
  13. Matériau de formation d'image selon la revendication 11, dans lequel ledit composé polymérisable a dans une molécule de celui-ci au moins deux groupes acryliques ou méthacryliques.
  14. Matériau de formation d'image selon la revendication 1 ou 2, dans lequel ladite couche de formation d'image comprend une couche de réticulation acide contenant un générateur d'acide et un composé de réticulation.
  15. Matériau de formation d'image selon la revendication 14, dans lequel ledit générateur d'acide est contenu en une quantité de 0,01 à 50 % en poids par rapport aux matières solides totales de ladite couche de réticulation acide.
  16. Matériau de formation d'image selon la revendication 14, dans lequel ledit agent de réticulation est contenu en une quantité de 5 à 70 % en poids par rapport aux matières solides totales de ladite couche de réticulation acide.
  17. Matériau de formation d'image selon la revendication 7, dans lequel ladite couche de formation d'image comprend une couche de réticulation acide contenant un générateur d'acide et un composé de réticulation.
  18. Matériau de formation d'image selon la revendication 17, dans lequel ledit générateur d'acide est contenu en une quantité de 0,01 à 50 % en poids par rapport aux matières solides totales de ladite couche de réticulation acide.
  19. Matériau de formation d'image selon la revendication 17, dans lequel ledit agent de réticulation est contenu en une quantité de 5 à 70 % en poids par rapport aux matières solides totales de ladite couche de réticulation acide.
  20. Matériau de formation d'image selon la revendication 1 ou 2 comprenant un composé décomposable par acide dont une liaison chimique peut être clivée, avec un acide agissant en tant que catalyseur, afin d'augmenter la solubilité de la couche de formation d'image dans une solution de développement alcaline.
  21. Matériau de formation d'image selon la revendication 7, comprenant un composé décomposable par acide dont une liaison chimique peut être clivée, avec un acide agissant en tant que catalyseur, afin d'augmenter la solubilité de la couche de formation d'image dans une solution de développement alcaline.
  22. Matériau de formation d'image selon la revendication 1 ou 2 comprenant un matériau de conversion de polarité qui peut être changé depuis le fait d'être lipophile vers le fait d'être hydrophile par la chaleur.
  23. Matériau de formation d'image selon la revendication 7, comprenant un matériau de conversion de polarité qui peut être changé depuis le fait d'être lipophile vers le fait d'être hydrophile par la chaleur.
  24. Absorbeur d'infrarouge représenté par la formule générale (1) comme suit :
    Figure 01170001
    dans laquelle formule : chacun de RF 1 et RF 2 représente indépendamment un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH,
    dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; chacun de X1 et X2 représente indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    Z1 représente un groupe heptaméthine, qui peut avoir un ou plusieurs substituants choisis parmi des groupes alkyle, des atomes d'halogène, des groupes amino, des groupes arylthio, des groupes alkylthio, des groupes aryloxy, des groupes alcoxy, des groupes barbiturique et des groupes thiobarbiturique, et qui peut inclure un cycle cyclohexène
    ou cyclopentène formé en liant mutuellement des substituants sur deux carbones méthine du groupe heptaméthine, lequel cycle peut en plus avoir un substituant choisi parmi des groupes alkyle et des atomes d'halogène ; et
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique.
  25. Absorbeur d'infrarouge représenté par la formule générale (2) comme suit :
    Figure 01180001
    dans laquelle formule : RF 3 représente un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; X3 représente -NH-, -O- ou -S- ; chacun de R12 et R13 représentent indépendamment un groupe alkyle ;
    chacun de X1 et X2 représente indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique ; et
    Z2 étant une chaíne polyméthine d'au moins 5 atomes de carbone.
  26. Absorbeur infrarouge représenté par la formule générale (3) comme suit :
    Figure 01190001
    dans laquelle formule : chacun de RF 4, RF 5, RF 6 et RF 7 représente indépendamment un substituant contenant du fluor ayant au moins 5 atomes de fluor ou un groupe alkyle, et au moins un de RF 4, RF 5, RF 6 et RF 7 représente un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; Z3 représente un groupe pentaméthine, qui peut avoir un substituant choisi parmi des atomes d'halogène, des groupes hydroxyle, des groupes alkyle ayant éventuellement un substituant supplémentaire, des groupes aryle ayant éventuellement un substituant supplémentaire et des groupes hétérocyclique, et qui peut également contenir un cycle cyclohexène ou cyclopentène formé en liant mutuellement des substituants sur deux carbones méthine du groupe pentaméthine, lequel cycle peut en plus avoir un substituant choisi parmi des groupes alkyle et des atomes d'halogènes ; et
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique.
  27. Absorbeur d'infrarouge comprenant une chaíne polyméthine d'au moins 5 atomes de carbone et un groupe alkyle d'au moins 16 atomes de carbone, ledit groupe alkyle étant lié à la chaíne polyméthine via l'un quelconque parmi l'azote, l'oxygène et le soufre, dans lequel ledit absorbeur d'infrarouge est représenté par la formule générale (4) comme suit :
    Figure 01210001
    dans laquelle formule : R14 représente un groupe alkyle d'au moins 16 atomes de carbone ; X3 représente -NH-, -O- ou -S- ; chacun de R12 et R13 représente indépendamment un groupe alkyle ; chacun de X1 et X2 représente indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique ; et
    Z2 étant une chaíne polyméthine d'au moins 5 atomes de carbone.
  28. Plaque d'impression planographique incluant un matériau de formation d'image applicable en mode thermique de la revendication 1 ou 2.
  29. Matériau de formation d'image applicable en mode thermique selon la revendication 2, dans lequel l'agent absorbeur d'infrarouge est représenté par la formule générale (1) comme suit :
    Figure 01220001
    dans laquelle formule : chacun de RF 1 et RF 2 représente indépendamment un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; chacun de X1 et X2 représente indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    Z1 représente un groupe heptaméthine, qui peut avoir un ou plusieurs substituants choisis parmi des groupes alkyle, des atomes d'halogène, des groupes amino, des groupes arylthio, des groupes alkylthio, des groupes aryloxy, des groupes alcoxy, des groupes barbiturique et des groupes thiobarbiturique, et qui peut inclure un cycle cyclohexène ou cyclopentène formé en liant mutuellement des substituants sur deux carbones méthine du groupe heptaméthine, lequel cycle peut en plus avoir un substituant choisi parmi des groupes alkyle et des atomes d'halogène ; et
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique.
  30. Matériau de formation d'image applicable en mode thermique selon la revendication 2, dans lequel l'agent absorbeur d'infrarouge est représenté par la formule générale (2) comme suit :
    Figure 01230001
    dans laquelle formule : RF 3 représentent un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou - (CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; X3 représente -NH-, -O- ou -S- ; chacun de R12 et R13 représente indépendamment un groupe alkyle ;
    chacun de X1 et X2 représentent indépendamment -CR9R10-, -S-, -Se-, -NR11-, -CH=CH- ou -O- ; R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy ou un atome d'halogène ; R1 à R8 peuvent représenter une pluralité d'atomes tels qu'au moins une des paires R1 et R3, R2 et R4, R5 et R7, R6 et R8, R1 et X1, et R2 et X2 peut se lier mutuellement afin de former un cycle à 5 membres ou cycle à 6 membres aliphatique, un cycle à 6 membres aromatique ou un cycle à 6 membres aromatique substitué ;
    R9 et R10 représentent chacun indépendamment un groupe alkyle, ou représentent =CH- qui sont combinés afin de former un cycle ; R11 représente un groupe alkyle ;
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique ; et
    Z2 étant une chaíne polyméthine d'au moins 5 atomes de carbone.
  31. Matériau de formation d'image applicable en mode thermique selon la revendication 2, dans lequel l'agent absorbeur d'infrarouge est représenté par la formule générale (3) comme suit :
    Figure 01240001
    dans laquelle formule : chacun de RF 4, RF 5, RF 6 et RF 7 représente indépendamment un substituant contenant du fluor ayant au moins 5 atomes de fluor ou un groupe alkyle, et au moins un de RF 4, RF 5, RF 6 et RF 7 représente un substituant contenant du fluor ayant au moins 5 atomes de fluor, le substituant contenant du fluor étant représenté par -(CH2)n(CF2)mCF3 ou -(CH2)n(CF2)(CF2)mH, dans lequel n représente un nombre entier de 0 à 6 et m représente un nombre entier de 2 à 16 ; Z3 représente un groupe pentaméthine, qui peut avoir un substituant choisi parmi des atomes d'halogène, des groupes hydroxyle, des groupes alkyle ayant éventuellement un substituant supplémentaire, des groupes aryle ayant éventuellement un substituant supplémentaire et des groupes hétérocyclique, et qui peut également contenir un cycle cyclohexène ou cyclopentène formé en liant mutuellement des substituants sur deux carbones méthine du groupe pentaméthine, lequel cycle peut en plus avoir un substituant choisi parmi des groupes alkyle et des atomes d'halogènes ; et
    X- représente un contre-ion nécessaire pour neutraliser une charge électrique.
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